Use of betulinic acid as a calcite inhibitor
By using betulinic acid as a calcite inhibitor and taking advantage of the properties of its functional groups, the problems of high difficulty in flotation separation of fluorite and calcite and poor selectivity of existing inhibitors have been solved, achieving efficient and low-toxicity flotation separation of fluorite ore.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- QINGHAI INST OF SALT LAKES OF CHINESE ACAD OF SCI
- Filing Date
- 2023-12-27
- Publication Date
- 2026-07-07
AI Technical Summary
The existing flotation separation of fluorite and calcite is difficult, and commonly used inhibitors have poor selectivity and require large amounts, which increases the difficulty of tailings particle settling treatment.
Betulinic acid is used as a calcite inhibitor. By utilizing the hydrophilicity and solidophilicity of its functional groups such as hydroxyl, carboxyl, and carbon six-membered ring, it selectively adsorbs calcite, reduces the adsorption of fluorite, and increases the difference in floatability between fluorite and calcite.
It achieves efficient separation of fluorite and calcite with a relatively small dosage, improves flotation efficiency, and reduces the risk of environmental pollution.
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Abstract
Description
Technical Field mineral resources
[0001] This invention belongs to the field of mineral processing technology, specifically relating to the application of betulinic acid as a calcite inhibitor and a flotation method for fluorite ore. Background Technology
[0002] Fluorite, also known as fluorspar, is a relatively common mineral in nature, its main component being calcium fluoride (CaF2). In the metallurgical industry, it is used as a flux in steelmaking to remove impurities; in the optical field, there is a significant demand for fluorite, and its artificially synthesized crystals can be grown to make various lenses. Fluorite often occurs alongside calcite, and flotation is commonly used in industry to separate the two. Both are calcium-bearing minerals and share the same active sites. Therefore, flotation separation between them is relatively difficult, and the addition of highly selective depressants during the flotation process is necessary.
[0003] Currently, commonly used depressants in fluorite flotation mainly include modified water glass and sodium hexametaphosphate. In addition, in recent years, mineral processing workers have discovered that organic depressants such as starch, sodium humate, and tannins can also be used as fluorite flotation depressants. Inorganic water glass remains the most widely used depressant in industry, but its poor selectivity and large dosage can lead to the suppression of some fluorite, increasing the difficulty of subsequent tailings particle settling treatment. Summary of the Invention
[0004] Betulinic acid, also known as betulinic acid, has the molecular formula C2. 30 H 48 O3, with a molecular weight of 456.71. Betulinic acid can be extracted from the leaves of Syzygium aromaticum, birch bark, and jujube kernels, or it can be chemically synthesized from betulinol. Betulinic acid has broad-spectrum antitumor activity with excellent selectivity and shows almost no toxicity to normal cells. It is currently widely used in the pharmaceutical field, but its application in mineral processing has not yet been reported. The inventors discovered that the betulinic acid molecule contains functional groups such as hydroxyl, carboxyl, and a six-membered carbon ring, which are both hydrophilic and polar groups, and have the potential to act as mineral inhibitors. This invention expands the application of betulinic acid in the field of mineral processing, particularly relating to the flotation separation of fluorite and calcite.
[0005] One of the objectives of this invention is to provide betulinic acid as a calcite inhibitor. The molecular formula of betulinic acid contains functional groups such as hydroxyl, carboxyl, and a six-membered carbon ring. These functional groups are both hydrophilic and fixophilic, giving betulinic acid a strong adsorption effect on calcite.
[0006] In some embodiments, the application includes: in the flotation process of fluorite ore, using betulinic acid to selectively adsorb calcite, thereby separating calcite from fluorite ore. Betulinic acid has a stronger adsorption effect on calcite in fluorite ore containing calcite, while it does not readily adsorb fluorite ore. Its excellent selective adsorption properties make it suitable for use as a calcite inhibitor in fluorite ore.
[0007] In some embodiments, the application includes: preparing a slurry of fluorite ore containing calcite, and then adding at least an inhibitor and a collector to the slurry for flotation, wherein the inhibitor includes betulinic acid.
[0008] In some embodiments, the application specifically includes: grinding and adjusting the fluorite ore containing calcite to obtain a slurry; adjusting the pH of the slurry to 8-10; and adding the inhibitor and collector to the slurry at the pH value for flotation.
[0009] In some embodiments, the amount of betulinic acid used in the flotation process is 500-1500 g / t. In the betulinic acid dosage described in this invention, g / t refers to the mass of betulinic acid, and t refers to the dry weight of the fluorite ore sample.
[0010] In some embodiments, the amount of collector used in the flotation process is 800-1500 g / t.
[0011] In some embodiments, the collector may be any fluorite ore collector in the prior art, such as sodium oleate, lauric acid, oxidized paraffin soap, etc., but is not limited thereto.
[0012] In some embodiments, the application further includes: performing one or more fine cleaning processes on the fluorite rough obtained by flotation, with a collector added in each fine cleaning process to obtain fluorite concentrate.
[0013] In some preferred embodiments, the amount of collector used in each selection is 300-800 g / t.
[0014] In some embodiments, the application further includes: performing one or more scavenging processes on the tailings obtained from flotation to obtain the final tailings.
[0015] In some embodiments, the minerals with a fineness of -74 micrometers (i.e., fineness below 74 micrometers) account for 60%-85% of the slurry.
[0016] In some embodiments, the concentration of solid minerals in the slurry is 30%-50%.
[0017] In some embodiments, the inhibitor is added to the slurry and stirred for 3-10 minutes before the collector is added.
[0018] In some embodiments, betulinic acid is dissolved in a methanol solution to prepare an inhibitor solution with a mass fraction of 0.5%, which is then added to the slurry.
[0019] The second objective of this invention is to provide a flotation method for fluorite ore, the flotation method comprising: crushing calcite-type fluorite ore to prepare a slurry, and then adding at least an inhibitor and a collector to the slurry for flotation; wherein the inhibitor includes betulinic acid.
[0020] In some embodiments, the fluorite ore flotation method specifically includes: grinding and adjusting the calcite-containing fluorite ore to obtain a slurry; adjusting the pH of the slurry to 8-10; and sequentially adding the inhibitor and collector to the slurry at the pH value for flotation.
[0021] In some embodiments, the amount of betulinic acid used in the flotation process is 500-1500 g / t.
[0022] In some embodiments, the amount of collector used in the flotation process is 800-1500 g / t.
[0023] In some embodiments, the collector may be any fluorite ore collector in the prior art, such as sodium oleate, lauric acid, oxidized paraffin soap, etc., but is not limited thereto.
[0024] In some embodiments, the fluorite flotation method further includes: performing one or more fine cleaning processes on the fluorite rough obtained from flotation, with a collector added in each fine cleaning process to obtain fluorite concentrate.
[0025] In some preferred embodiments, the amount of collector used in each selection is 300-800 g / t.
[0026] In some embodiments, the fluorite flotation method further includes: performing one or more scavenging processes on the tailings obtained from flotation to obtain the final tailings.
[0027] In some embodiments, the minerals with a fineness of -74 micrometers account for 60%-85% of the slurry.
[0028] In some embodiments, the concentration of solid minerals in the slurry is 30%-50%.
[0029] In some embodiments, the inhibitor is added to the slurry and stirred for 3-10 minutes before the collector is added.
[0030] In some embodiments, betulinic acid is dissolved in a methanol solution to prepare an inhibitor solution with a mass fraction of 0.5%, which is then added to the slurry.
[0031] In some embodiments, the CaF2 grade obtained by the fluorite flotation method is above 88.12%, and the CaF2 recovery rate is above 89.36%.
[0032] A third objective of this invention is to provide a calcite inhibitor for fluorite flotation, wherein the inhibitor comprises betulinic acid.
[0033] Compared with existing technologies, the present invention has at least the following beneficial effects: The molecular structure of betulinic acid contains functional groups such as hydroxyl, carboxyl, and carbon six-membered rings. These functional groups are both hydrophilic and fixophilic groups, exhibiting strong adsorption for calcite. This makes betulinic acid readily adsorbed onto calcite but not readily adsorbed onto fluorite. This excellent selectivity amplifies the difference in floatability between calcite and fluorite, resulting in a more selective and effective flotation method for fluorite based on betulinic acid. Compared to commonly used depressants in existing technologies such as water glass, betulinic acid, when used as a depressant for fluorite flotation, exhibits stronger selectivity and can achieve better flotation results with lower dosage. Furthermore, betulinic acid is non-toxic and causes minimal environmental pollution. Detailed Implementation
[0034] The technical solutions of the present invention will be described in detail below with reference to specific embodiments, so that those skilled in the art can better understand and implement the technical solutions of the present invention. The specific functional details disclosed herein should not be construed as limiting, but are merely intended to form the basis of the claims and to teach those skilled in the art to employ the representative basis of the invention in different ways in any suitable detailed embodiment.
[0035] Example 1
[0036] In this embodiment, betulinic acid is dissolved in methanol solution to obtain an inhibitor solution with a mass fraction of 0.5% for later use;
[0037] The fluorite ore used in this embodiment is calcite-type fluorite ore, and its composition and the mass percentage of each component are as follows: CaF2 18.75%, CaCO3 9.2%, SiO2 49.21%. The specific operating steps are as follows:
[0038] First, take 200g of fluorite ore, grind it to a -74μm content of 75%, add it to a 0.5L flotation cell, and adjust the pH of the pulp to 8.5;
[0039] Add the prepared inhibitor solution at a dosage of 800 g / t betulinic acid, stir for 5 minutes, then add 1200 g / t sodium oleate for roughing, obtaining rough concentrate and rough tailings. Add 600 g / t sodium oleate to the rough concentrate for the first cleaning, obtaining primary cleaning concentrate and primary cleaning tailings. Add 1500 g / t sodium oleate to the primary cleaning concentrate for the second cleaning, obtaining final concentrate and secondary cleaning tailings. Perform scavenging on the rough tailings to obtain scavenged concentrate and final tailings. No reagents are added during the scavenging operation. The flotation results are shown in Table 1.
[0040] Example 2
[0041] The inhibitor used in this embodiment is the same as in Embodiment 1.
[0042] The fluorite ore used in this embodiment is calcite-type fluorite ore, and its composition and the mass percentage of each component are as follows: CaF2 21.03%, CaCO3 8.21%, SiO2 50.12%; the specific operating steps are as follows:
[0043] Take 1000g of fluorite ore, grind it to -74μm content of 75%, add it to a 3L flotation cell, and adjust the pH of the slurry to 9;
[0044] Add the prepared inhibitor solution to the slurry at a dosage of 600 g / t betulinic acid. After stirring for 5 minutes, add 1300 g / t sodium oleate to begin roughing. Roughing yields rough concentrate and rough tailings. Add 500 g / t sodium oleate to the rough concentrate for the first cleaning process, yielding primary cleaning concentrate and primary cleaning tailings. Add 150 g / t sodium oleate to the primary cleaning concentrate for the second cleaning process, yielding final concentrate and secondary cleaning tailings. Return the secondary cleaning tailings to the previous cleaning operation. Perform a scavenging operation on the rough tailings without adding reagents. The flotation results are shown in Table 1.
[0045] Example 3
[0046] The inhibitor used in this embodiment is the same as in Embodiment 1.
[0047] The fluorite ore used in this embodiment is calcite-type fluorite ore, and its composition and the mass percentage of each component are as follows: CaF2 17.25%, CaCO3 11.33%, SiO2 51.01%. The specific operating steps are as follows:
[0048] First, take 300g of fluorite ore, grind it to a -74μm content of 70%, add it to a 0.75L flotation cell, and adjust the pH of the pulp to 9;
[0049] Add inhibitor solution to the slurry at a dosage of 750 g / t betulinic acid. After stirring for 5 minutes, add 1600 g / t sodium oleate to begin roughing. Roughing yields rough concentrate and rough tailings. Add 500 g / t sodium oleate to the rough concentrate for the first cleaning process, yielding primary cleaning concentrate and primary cleaning tailings. Add 200 g / t sodium oleate to the primary cleaning concentrate for the second cleaning process, yielding final concentrate and secondary cleaning tailings. Return the secondary cleaning tailings to the previous cleaning operation. Perform a scavenging operation on the rough tailings without adding reagents. The flotation results are shown in Table 1.
[0050] Example 4
[0051] The inhibitor used in this embodiment is the same as in Embodiment 1.
[0052] The fluorite ore used in this embodiment is calcite-type fluorite ore, and its composition and the mass percentage of each component are as follows: CaF2 18.5%, CaCO3 9.1%, SiO2 50.21%. The specific operating steps are as follows:
[0053] First, take 250g of fluorite ore, grind it to -74μm content of 75%, add it to a 0.5L flotation cell, and adjust the pH of the pulp to 9.5 with sodium hydroxide;
[0054] Add inhibitor solution to the slurry at a dosage of 650 g / t betulinic acid. After stirring for 5 minutes, add 1300 g / t sodium oleate to begin roughing. Roughing yields rough concentrate and rough tailings. Add 400 g / t sodium oleate to the rough concentrate for the first cleaning process, yielding primary cleaning concentrate and primary cleaning tailings. Add 150 g / t sodium oleate to the primary cleaning concentrate for the second cleaning process, yielding final concentrate and secondary cleaning tailings. Return the secondary cleaning tailings to the previous cleaning operation. Perform a scavenging operation on the rough tailings without adding reagents. The flotation results are shown in Table 1.
[0055] Example 5
[0056] The inhibitor used in this embodiment is the same as in Embodiment 1.
[0057] The fluorite ore used in this embodiment is calcite-type fluorite ore, and its composition and the mass percentage of each component are as follows: CaF2 18.59%, CaCO3 12.31%, SiO2 49.12%. The specific operating steps are as follows:
[0058] First, take 200g of fluorite ore, grind it to -74μm content of 75%, add it to a 0.5L flotation cell, and adjust the pH of the pulp to 9 with sodium hydroxide;
[0059] Add inhibitor solution to the slurry at a dosage of 500 g / t betulinic acid. After stirring for 3 minutes, add 1300 g / t sodium oleate to begin roughing. Roughing yields rough concentrate and rough tailings. Add 600 g / t sodium oleate to the rough concentrate for the first cleaning process, yielding primary cleaning concentrate and primary cleaning tailings. Add 150 g / t sodium oleate to the primary cleaning concentrate for the second cleaning process, yielding final concentrate and secondary cleaning tailings. Return the secondary cleaning tailings to the previous cleaning operation. Perform a scavenging operation on the rough tailings without adding reagents. The flotation results are shown in Table 1.
[0060] Example 6
[0061] The dosage of betulinic acid was 500 g / t, the pulp pH was 8, the proportion of minerals with a fineness of -74 microns was 60%, and other conditions were the same as in Example 1. The flotation results are shown in Table 1.
[0062] Example 7
[0063] The dosage of betulinic acid was 1500 g / t, the pulp pH was 10, the proportion of minerals with a fineness of -74 microns was 85%, and other conditions were the same as in Example 1. The flotation results are shown in Table 1.
[0064] Comparative Example 1
[0065] The only difference between Comparative Example 1 and Example 1 is that the 800g / t betulinic acid inhibitor used above is replaced with 1800g / t water glass. The same procedure is followed as in Example 1, and the flotation results are shown in Table 1.
[0066] Comparative Example 2
[0067] The only difference between Comparative Example 2 and Example 2 is that the 600g / t betulinic acid inhibitor used in Example 2 was replaced with 2000g / t water glass. The rest of the process was the same as in Example 2. The flotation results are shown in Table 1.
[0068] Comparative Example 3
[0069] The only difference between Comparative Example 3 and Example 3 is that the 750 g / t betulinic acid inhibitor was replaced with 2000 g / t water glass. The rest of the process was the same as in Example 3, and the flotation results are shown in Table 1.
[0070] Comparative Example 4
[0071] The only difference between Comparative Example 4 and Example 4 is that 650 g / t of betulinic acid was replaced with 1800 g / t of water glass. The rest of the process was the same as in Example 4. The flotation results are shown in Table 1.
[0072] Comparative Example 5
[0073] The only difference between Comparative Example 5 and Example 1 is that 500 g / t of betulinic acid was replaced with 2000 g / t of water glass. The rest of the process was the same as in Example 5. The flotation results are shown in Table 1.
[0074] Comparative Example 6
[0075] The only difference from Example 6 is that betulinic acid is replaced with water glass, with the same amount used. The flotation effect is shown in Table 1.
[0076] Comparative Example 7
[0077] The only difference from Example 7 is that betulinic acid is replaced with water glass, with the same amount used. The flotation effect is shown in Table 1.
[0078] Table 1. Flotation effects of the flotation methods in the examples and comparative examples.
[0079]
[0080]
[0081] In summary, in the flotation process of calcite-type fluorite ore, the flotation method based on betulinic acid achieved good flotation results with a smaller amount of betulinic acid used.
[0082] All aspects, embodiments, features, and examples of this invention are to be regarded as illustrative in all respects and are not intended to limit the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will become apparent to those skilled in the art without departing from the spirit and scope of the invention as claimed.
[0083] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.
[0084] Although the invention has been described with reference to illustrative embodiments, those skilled in the art will understand that various other changes, omissions, and / or additions can be made without departing from the spirit and scope of the invention, and that elements of the embodiments can be substituted with substantially equivalents. Furthermore, many modifications can be made without departing from the scope of the invention to adapt particular situations or materials to the teachings of the invention. Therefore, this invention is not intended to be limited to the specific embodiments disclosed for carrying out the invention, but rather is intended to encompass all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated otherwise, any use of the terms first, second, etc., does not indicate any order or importance, but is used to distinguish one element from another.
Claims
1. The application of betulinic acid as a calcite inhibitor, characterized in that, include: In the flotation process of fluorite ore, betulinic acid is used to selectively adsorb calcite, thereby separating calcite from fluorite ore.
2. The application according to claim 1, characterized in that, include: Fluorite ore containing calcite is prepared into a slurry, and then at least an inhibitor and a collector are added to the slurry for flotation, wherein the inhibitor includes betulinic acid.
3. The application according to claim 2, characterized in that, Specifically, it includes: The fluorite ore containing calcite was successively ground and slurry-prepared to obtain a slurry; Adjust the pH of the slurry to 8-10; The inhibitor and collector are added sequentially to the slurry at the specified pH value for flotation.
4. The application according to claim 3, characterized in that: In the flotation process, the amount of betulinic acid used is 500-1500 g / t.
5. The application according to claim 3, characterized in that: In the flotation process, the amount of collector used is 800-1500 g / t.
6. The application according to claim 3, characterized in that: The collector includes one or more of sodium oleate, lauric acid, and oxidized paraffin soap.
7. The application according to claim 3, characterized in that, Also includes: The fluorite rough obtained from flotation is subjected to one or more fine cleaning processes, with a collector added in each fine cleaning process to obtain fluorite concentrate.
8. The application according to claim 7, characterized in that: In each selection process, the amount of collector used is 300-800g / t.
9. The application according to claim 3, characterized in that, Also includes: The tailings obtained from flotation are subjected to one or more scavenging processes to obtain the final tailings.
10. The application according to claim 3, characterized in that: In the slurry, minerals with a fineness of less than 74 micrometers account for 60%-85%.
11. The application according to claim 3, characterized in that: The concentration of solid minerals in the slurry is 30%-50%.
12. The application according to claim 3, characterized in that: After adding the inhibitor to the slurry, stir for 3-10 minutes, and then add the collector.
13. The application according to claim 3, characterized in that: A 0.5% (w / w) inhibitor solution was prepared by dissolving betulinic acid in methanol and then added to the slurry.
14. A flotation method for fluorite ore, characterized in that, include: Fluorite ore containing calcite is crushed and made into a slurry. Then, at least an inhibitor and a collector are added to the slurry for flotation. The inhibitor includes betulinic acid.
15. The fluorite flotation method according to claim 14, characterized in that, Specifically, it includes: The fluorite ore containing calcite was successively ground and slurry-prepared to obtain a slurry; Adjust the pH of the slurry to 8-10; The inhibitor and collector are added sequentially to the slurry at the specified pH value for flotation.
16. The fluorite ore flotation method according to claim 15, characterized in that: In the flotation process, the amount of betulinic acid used is 500-1500 g / t.
17. The fluorite ore flotation method according to claim 15, characterized in that: In the flotation process, the amount of collector used is 800-1500 g / t.
18. The fluorite ore flotation method according to claim 15, characterized in that: The collector includes one or more of sodium oleate, lauric acid, and oxidized paraffin soap.
19. The fluorite ore flotation method according to claim 15, characterized in that, Also includes: The fluorite rough obtained from flotation is subjected to one or more fine cleaning processes, with a collector added in each fine cleaning process to obtain fluorite concentrate.
20. The fluorite ore flotation method according to claim 19, characterized in that: In each selection process, the amount of collector used is 300-800g / t.
21. The fluorite ore flotation method according to claim 15, characterized in that, Also includes: The tailings obtained from flotation are subjected to one or more scavenging processes to obtain the final tailings.
22. The fluorite ore flotation method according to claim 15, characterized in that: In the slurry, minerals with a fineness of less than 74 micrometers account for 60%-85%.
23. The fluorite ore flotation method according to claim 15, characterized in that: The concentration of solid minerals in the slurry is 30%-50%.
24. The fluorite flotation method according to claim 15, characterized in that: After adding the inhibitor to the slurry, stir for 3-10 minutes, and then add the collector.
25. The fluorite ore flotation method according to claim 15, characterized in that: A 0.5% (w / w) inhibitor solution was prepared by dissolving betulinic acid in methanol and then added to the slurry.
26. The fluorite ore flotation method according to any one of claims 14-25, characterized in that: The flotation method yields a CaF2 grade of 88.12% or higher and a CaF2 recovery rate of 89.36% or higher.
27. A calcite depressant for fluorite ore flotation, characterized in that: The inhibitors include betulinic acid.